CA2567841C

CA2567841C - Process for preparing water-soluble articles

Info

Publication number: CA2567841C
Application number: CA2567841A
Authority: CA
Inventors: Francesc Ayats; Jordi Salvador; Frederic Moreux
Original assignee: Reckitt Benckiser NV
Current assignee: Reckitt Benckiser Finish BV
Priority date: 2004-06-11
Filing date: 2005-06-09
Publication date: 2013-02-12
Anticipated expiration: 2025-06-09
Also published as: US20080014392A1; ZA200609437B; PL1756257T3; WO2005121302A1; US20090196891A1; GB0413053D0; EP1756257A1; EP2752481A1; BRPI0511902A; WO2005121302A8; EP1756257B1; US20090196892A1; GB2414958A; CN1965071A; US20170101610A1; AU2005252429A1; ES2472730T3; CA2567841A1

Abstract

A process for preparing a water-soluble article comprising a water-soluble primary thermoformed component (2) and a water-soluble secondary component (3) arranged therein comprises: (a) forming the primary component (2) into a pocket, by thermoforming in the cavity of a thermoforming mould; (b) adding the secondary component (3) to the mould; (c) introducing the contents (4) of the primary component into the pocket; and (d) sealing the primary component (2), characterised in that the cavity of the thermoforming mould has a recess to receive the secondary component.

Description

2 PCT/GB2005/002264 PROCESS FOR PREPARING WATER-SOLUBLE ARTICLES

The present invention relates to a process for producing a water-soluble article comprising a water-soluble, primary (or "first") thermoformed component and a water-soluble, secondary (or "second") component arranged therein. It also relates to an article obtainable by such a process.
Thermoforming is a well-known technique for preparing arti-cles from a polymer. It generally comprises heating a poly-meric composition, which can be in the form of, for example, a film, to above its softening temperature and thermally de-forming the composition in a male or female mould.

It is also known to package chemical compositions, particu-larly those which may be of a hazardous or irritant nature, in films. If such compositions are held within water-soluble films forming a container around the compositions, the containers can simply be added to water in order to dis-solve or disperse the composition into the water.

WO 92/17382 discloses a package containing an agrochemical comprising a first sheet of non-planar water-soluble or wa-ter-dispersible material and a second sheet of water-soluble or water-dispersible material superposed on the first sheet and sealed to it.

However, this package can only contain a single composition which is compatible with the film. It cannot be used for two compositions which are incompatible with each other or for compositions which are incompatible with the water-soluble or water-dispersible material. For example, WO

92/17382 states that when the package contains the liquid, the liquid must be an organic liquid which contains less than 2 to 3% of water to ensure that it does not attack the film forming the package and cause leakage.

The present invention provides a process for preparing a water-soluble article comprising a water-soluble primary thermoformed component and a water-soluble secondary component arranged therein, which comprises:-(a) forming the primary component into a pocket, by thermoforming in the cavity of a thermoforming mould;

(b) adding the secondary component to the mould;

(c) introducing the contents of the primary component into the pocket; and (d) sealing the primary component, characterised in that the cavity of the thermoforming mould has a recess to receive the secondary component.

According to one aspect of the present invention, there is provided a process for preparing a water-soluble article comprising a water-soluble primary thermoformed component and a water-soluble secondary component arranged inside the primary component, which comprises: (a) forming the primary component into a pocket, by thermoforming in a cavity of a thermoforming mould that also has a recess to receive the secondary component; (b) introducing the secondary component into the inside of the pocket such that it is received in said recess; (c) afterwards, introducing contents of the primary component into the pocket; and (d) sealing the primary component, wherein the contents of the primary component are granulated and/or particulate solid(s), and tight packing of said contents into the primary component ensures that the secondary component is fixed in position in the primary component.

- 2a -The present invention also provides a water-soluble article comprising a water-soluble primary component which is a thermoformed container containing a primary composition, and a water-soluble secondary component arranged on the inside thereof.

According to another aspect of the present invention, there is provided a water-soluble article comprising a water-soluble primary component which is a thermoformed container containing a granulate and/or particulate solid primary composition, and a water-soluble secondary component arranged on the inside of the thermoformed container in a recess thereof, fixing of the secondary component in position in the primary component being ensured by tight packing of said solid primary composition into said primary component.

Most preferably the contents of the primary component are solid, e.g. such as a granulate/particulate.

-3-Generally the contents of the primary component are tightly packed so that the secondary component is fixed in position in the primary component. This fixed/reliable positioning has several advantages.

Firstly it ensures that in the sealing stage of the primary component, no detrimental interaction occurs with the secon-dary component. Thus any potentially detrimental physical issues, such as the disturbance/rupture of the secondary component are obviated, as the positioning of the secondary component away from the area of the sealing portion is en-sured. This is particularly important when the secondary component contains components which would (if not kept sepa-rate) detrimentally react with the contents of the primary component. It also ensures that sealing of the primary com-ponent is not detrimentally affected by the presence of the secondary component.

Additionally the shape of the final article is predictable:
in certain uses, such as in an automatic dishwasher, there is a requirement that the article has a certain shape so that it may be accommodated in the dosing chamber of the dishwasher. With the reliable location of the secondary component within the article produced in accordance with the present invention a predicted form is achieved. Further the predictable form ensures that the article can be packed (e.g. in boxes/pouches for sale to a consumer) with greatly reduced interaction between articles since each article has the same uniform shape.

Furthermore where the primary component is transparent and where the secondary component has a contrasting appearance

-4-to the contents of the primary component the overall aes-thetics of the article can be guaranteed. This is particu-larly important where companies have recognised / associated shapes or patterns: it ensures the correct appearance of the article such that the consumer correctly connects the arti-cle with the company.

The present invention provides a convenient process for pre-paring an article comprising a thermoformed primary compo-nent, which has a secondary component arranged therein.

While it may well be possible to prepare an article by pre-paring the initial primary component by thermoforming and then attaching the secondary component thereto using, for example, an adhesive, the process of the present invention provides a process which can be carried out in a single step, thus eliminating the need to use separate machines.
The primary component, prior to being placed in or over the thermoforming mould, may be of any shape or form. The pri-mary component may, for example, be in the form of a rigid sheet or a flexible film. The finally formed water-soluble article may be, for example, in the form of a strip of a sheet or film. Individual compositions may then be removed from the sheet or film for individual use. Perforations in the sheet or film may be used to assist separation.

Ideally the primary component is a film which is thermo-formed in the mould, thus becoming the primary thermoformed component. Preferably the film of the primary component is formed into a pocket surrounded by a sealing portion. The pocket may be closed, for example by placing a film on top of the filled pocket and across the sealing portion and sealing the films together at the sealing portion.

Most desirably in the present invention the primary compo-nent is a container. The secondary component is arranged on the inside of the container.

The film may be a single film, or a laminated film as dis-closed in GB-A-2,244,258. While a single film may have pin-holes, the two or more layers in a laminate are unlikely to have pinholes which coincide. The film is water-soluble (which term is taken to include water-dispersible).

The term "water-soluble" when used herein means that when used in a washing machine, such as a fabric or dish washing machine, the water-soluble aspects of the article are sub-stantially (greater than 70%, ideally greater than 85%) dis-solved or dispersed into the water. This can be tested by placing the article in 10 litres of agitated water at 45 C
for 40 minutes and measuring any un-dissolved or non-disintegrated pieces of the parts of the article, which are water-soluble, that are left.

The film may be produced by any process, for example by ex-trusion and blowing or by casting. The film may be unori-ented, monoaxially oriented or biaxially oriented. If the layers in the film are oriented, they usually have the same orientation, although their planes of orientation may be different if desired.
The layers in a laminate may be the same or different. Thus they may each comprise the same polymer or a different poly-mer. If it is desired to have a water-soluble laminated film, each of the layers should be water-soluble.

Examples of water-soluble polymers which may be used in a single layer film or in one or more layers of a laminate are poly(vinyl alcohol) (PVOH) and cellulose derivatives such as hydroxypropyl methyl cellulose (HPMC). An example of a pre-ferred PVOH is ethoxylated PVOH. The PVOH may be partially or fully alcoholised or hydrolysed. For example it may be from 40 to 100%, preferably from 70 to 92%, more preferably about 88% or about 92%, alcoholised or hydrolysed. The de-gree of hydrolysis is known to influence the temperature at which the PVOH starts to dissolve in water. 88% hydrolysis corresponds to a film soluble in cold (ie room temperature) water, whereas 92% hydrolysis corresponds to a film soluble in warm water.

The thickness of the film used to produce the pocket is preferably 40 to 300 m, more preferably 70 to 200 m, espe-cially 80 to 160 m, more especially 90 to 150 m and most es-pecially 90 to 120 m.

In a thermoforming process the primary component, preferably a film, may be drawn down or blown down into a mould. Thus, for example, the primary component is heated to the thermo-forming temperature using a thermoforming heater plate as-sembly, and then drawn down under vacuum or blown down under pressure into the mould. Plug-assisted thermoforming and pre-stretching the film, for example by blowing the film away from the mould before thermoforming, may, if desired, be used. One skilled in the art can choose an appropriate temperature, pressure or vacuum and dwell time to achieve an appropriate pocket. The amount of vacuum or pressure and the thermoforming temperature used depend on the thickness and porosity of the film and on the polymer or mixture of polymers being used. The use of vacuum has been found to aid the drawing of the film into the recess of the thermo-forming cavity. Thermoforming of PVOH films is known and described in, for example, WO 00/55045.

A suitable forming temperature for PVOH or ethoxylated PVOH
is, for example, from 90 to 130 C, especially 90 to 120 C.
A suitable forming pressure is, for example, 69 to 138kPa (10 to 20 p.s.i.), especially 83 to 117kPa (12 to 17 p.s.i.). A suitable forming vacuum is 0 to 4kPa (0 to 40 mbar), especially 0 to 2kPa (0 to 20mbar). A suitable dwell time is, for example, 0.4 to 2.5 seconds, especially 2 to 2.5 seconds.

While desirably conditions are chosen within the above ranges, it is possible to use one or more of these parame-ters outside the above ranges, although it may be necessary to compensate by changing the values of the other two pa-rameters.

Where a pocket is formed from the primary component the sec-ondary component may be added into the recess. The addition is preferably performed in a mechanised technique, e.g. by using a robot arm.

The secondary component is most preferably a pre-formed shape. Generally the shape is such that the secondary com-ponent is suitably received in the recess of the thermoform-ing cavity. Preferred examples of suitable shapes include spheres, ovoids and other 3-dimensional shapes having a curved face (with the curved face preferably being disposed adjacent to the inside of the recess). Conversely the re-cess is preferably curved and most preferably is compli-mentery to the secondary component.

The secondary component may be any water-soluble components.
The term "water-soluble" again includes water-dispersible.

Thus, for example, the secondary component may be in the form of a solid, such as a compressed solid, for example in the form of a ball or pill. It may also itself be a con-tainer containing a secondary composition. For example it may comprise a polymeric film containing a secondary compo-sition such as a solid, a gel or a liquid. Such a container may be previously prepared by a thermoforming technique such as that discussed above. It may also be prepared by other means, for example by vertical form fill sealing, injection moulding or blow moulding.
When the pocket is formed from the primary component it is preferably filled with a desired composition before sealing.
The pocket is generally completely filled. The composition may be a solid. For example, it may be a particulate solid or a granulated solid. The composition may have more than one phase. For example it may comprise a plurality of lay-ers of differing (either aesthetically or chemically) compo-sitions. It may also comprise a liquid composition and a separate solid composition, for example in the form of a ball, pill or speckles.

After the pocket has been filled it is closed, for example by placing a film on top of the filled pocket and across the sealing portion, and sealing the films together at the seal-ing portion. This film may be a single-layered film but is desirably laminated to reduce the possibility of pinholes allowing leakage through the film. The film may be the same or different as the film forming the pocket. Examples of suitable films are those given for the film forming the pocket.
Desirably the covering film has a thickness which is less than that of the film used for forming a pocket because it would not generally be stretched so localised thinning of the sheet will not occur. It is also desirable to have a thickness which is less than that of the film used to form a pocket to ensure a sufficient heat transfer through the film to soften the pocket film if heat sealing is used.

The thickness of the covering film is generally from 20 to 160 m, preferably from 40 to 100 m, such as 40 to 80 m or 50 to 60 m.

The films may be sealed together by any suitable means, for example by means of an adhesive or by heat sealing. Other methods of sealing include infra-red, radio frequency, ul-trasonic, laser, solvent (such as water), vibration and spin welding. An adhesive such as an aqueous solution of PVOH
may also be used. The seal 'desirably is water-soluble if the containers are water-soluble. The presence of a coating on the sealing portion of the film could hinder or prevent sealing and could cause a reduction in seal strength.

Therefore, in the present invention, the sealing portion is preferably left uncoated by the coating composition.

If heat sealing is used, a suitable sealing temperature is, for example, 120 to 195 C, for example 140 to 150 C. A
suitable sealing pressure is, for example, from 250 to 600kPa. Examples of sealing pressures are 276 to 552kPa (40 to 80 p.s.i.), especially 345 to 483kPa (50 to 70 p.s.i.) or 400 to 800kPa (4 to 8 bar), especially 500 to 700kPa (5 to 7 bar) depending on the heat sealing machine used. Suitable sealing dwell times are 0.4 to 2.5 seconds.

One skilled in the art can use an appropriate temperature, pressure and dwell time to achieve a seal of the desired in-tegrity. While desirably conditions are chosen within the above ranges, it is possible to use one or more of these pa-rameters outside the above ranges, although it might be nec-essary to compensate by changing the values of the other two parameters.

If the primary composition or secondary composition is in-compatible with the films enclosing them, steps have to be taken to improve the compatibility. For example, if the films are water-soluble, the amount of free water in the compositions may be reduced. In particular, an electrolyte or gelling agent may be added. Alternatively a coating may be applied on the inside of the films, for example as dis-closed in WO 00/64667 or by coating the inside of the pock-ets after they have been thermoformed but before they have been filled.

The primary composition and the composition constituting the secondary component may be the same or different. If they are different they may, nevertheless, have one or more indi-vidual components in common. The present invention is espe-cially advantageous when the primary composition and the secondary composition are incompatible with each other since they are separated. It is also advantageous if one of the compositions is incompatible with the components contacting the other composition. For example, the secondary composi-tion may be a composition which is incompatible with the film forming the container containing the primary composi-tion when the secondary composition is itself held within a film. Similarly the primary composition may be a composi-tion which is incompatible with the secondary component or the film containing the secondary composition.

In a thermoforming process air must be evacuated from under-neath the primary component as it is being thermoformed. In particular the mould may, for example, be roughened to as-sist good air evacuation.

Preferably the secondary component should not be placed in a position where a substantial thinning of the primary compo-nent can occur if it is in the form of a film. Desirably, therefore, air is withdrawn from the sides and corners of the mould as well as, preferably, the bottom of the mould.
The mould contains a recess which is dimensioned so as to accept the secondary component. This is especially advanta-geous when the secondary component is in the form of a ball since it can simply roll into the recess. The recess may be in any part of the mould, but is desirably near the bottom of the mould, for example on the bottom surface of the mould. It may be at the centre of the bottom surface, or may be off-set to one side. Preferably the depth of the re-cess is adjustable to accommodate secondary components of varying size. Generally the recess is based on a portion of a sphere / ovoid. The recess is typically about 4mm deep (e.g. 4.5mm) and about 13mm wide.

During the thermoforming process the primary component, which is usually a polymer, has an elevated temperature. By an appropriate choice of thermoforming temperature and of the secondary component, the secondary component will stick to the primary component. This is especially the case when, for example, the secondary component itself comprises a polymeric film which will be heated to a certain extent by the elevated temperatures within the thermoforming machine or by the contacting of the heated primary component. The mould may also be formed such that the cooling pipes gener-ally used in thermoforming moulds do not cool the area di-rectly under the secondary component. Alternatively the mould may be formed such that heating, e.g. RF welding, heats the area under the secondary component to aid adher-ence to the primary component.

Alternatively the secondary component may have an adhesive applied thereto before or after it is placed in the cavity of the thermoforming mould. A suitable adhesive may, for example, be a polymer which is heated in the thermoforming mould, or a component such as water which can act as an ad-hesive when it contacts the primary component, especially when the primary component is water-soluble. Preferably the primary and secondary components are formed from or are coated with the same water-soluble polymer, this aids adhe-sion, especially in the presence of water. The adhesive may, for example, be a heat activated adhesive or coating.
The secondary component may also be held on the primary com-ponent by mechanical adhesion by ensuring that the primary component flows around and at least partially encloses the secondary component.

The primary and secondary compositions may independently be any compositions which are intended to be released in an aqueous environment. Thus, for example, either or both com-positions may be agrochemical compositions such as a plant protection agent, for instance a pesticide such as an insec-ticide, fungicide, herbicide, acaricide, or nematocide, a plant growth regulator or a plant nutrient. Such composi-tions are generally packaged in total amounts of from 0.1g to 7kg, preferably 1 to 5kg, when in solid form. When in liquid or gelled form, such compositions are generally pack-aged in total amounts of from lml to 10 litres, preferably 0.1 to 6 litres, especially from 0.5 to 1.5 litres.

The primary and secondary compositions may also independ-ently be fabric care, surface care or dishwashing composi-tions. Thus, for example, it may be a dishwashing, water-softening, laundry or detergent composition, or a rinse aid.
Such compositions may be suitable for use in a domestic washing machine. The primary and secondary compositions may also independently be a disinfectant, antibacterial or anti-septic composition, or a refill composition for a trigger-type spray. Such compositions are generally packaged in to-tal amounts of from 5 to 100g, especially from 15 to 40g.

For example, a dishwashing composition may weigh from 15 to 30g, a water-softening composition may weigh from 15 to 40g.
The primary composition and the secondary composition may be appropriately chosen depending on the desired use of the ar-ticle.

If the article is for use in laundry washing, the primary composition may comprise, for example, a detergent, and the secondary composition may comprise a bleach, stain remover, water-softener, enzyme or fabric conditioner. The article may be adapted to release the compositions at different times during the dish washing cycle. For example, a bleach or fabric conditioner is generally released at the end of a wash, and a water-softener is generally released at the start of a wash. An enzyme may be released at the start or the end of a wash.

If the article is for use as a fabric conditioner, the pri-mary composition may comprise a fabric conditioner and the secondary component may comprise an enzyme which is released before or after the fabric conditioner in a rinse cycle.

If the article is for use in dish washing the primary compo-sition may comprise a detergent and the secondary composi-tion may comprise a water-softener, enzyme, rinse aid, bleach or bleach activator. The article may be adapted to release the compositions at different times during the wash.
For example, a rinse aid, bleach or bleach activator is preferably released at the end of a wash, and a water-softener or enzyme is generally released at the start of a wash.

The remaining ingredients of the primary and secondary com-positions depend on the use of the compositions. Thus, for example, the compositions may independently contain surface active agents such as an anionic, nonionic, cationic, ampho-teric or zwitterionic surface active agents or mixtures thereof.

Examples of anionic surfactants are straight-chained or branched alkyl sulfates and alkyl polyalkoxylated sulfates, also known as alkyl ether sulfates. Such surfactants may be produced by the sulfation of higher Ce-C20 fatty alcohols.

Examples of primary alkyl sulfate surfactants are those of formula:
ROS03-M+
wherein R is a linear C8-C2o hydrocarbyl group and M is a wa-ter-solubilising cation. Preferably R is C10-C16 alkyl, for example C12-C14, and M is alkali metal such as lithium, sodium or potassium.

Examples of secondary alkyl sulfate surfactants are those which have the sulfate moiety on a "backbone" of the mole-cule, for example those of formula:

CH3 (CH2) n (CHOS03 M) (CH2) mCH3 wherein m and n are independently 2 or more, the sum of m+n typically being 6 to 20, for example 9 to 15, and M is a wa-ter-solubilising cation such as lithium, sodium or potas-sium.
Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate surfactants of formulae:

CH3 (CH2) (CHOS03-M+) CH3 and CH3 (CH2) x (CHOS03-M+) CH2CH3 for the 2-sulfate and 3-sulfate, respectively. In these formulae x is at least 4, for example 6 to 20, preferably 10 to 16. M is cation, such as an alkali metal, for example lithium, sodium or potassium.

Examples of alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the formula:

RO (C2H40) S03-M+
wherein R is a C8-C20 alkyl group, preferably C1o-C18 such as a C12-C16, n is at least 1, for example from 1 to 20, preferably 1 to 15, especially 1 to 6, and M is a salt-forming cation such as lithium, sodium, potassium, ammonium, alkylammonium or alkanolammonium. These compounds can provide especially desirable fabric cleaning performance benefits when used in combination with alkyl sulfates.

The alkyl sulfates and alkyl ether sulfates will generally be used in the form of mixtures comprising varying alkyl chain lengths and, if present, varying degrees of alkoxyla-tion.

Other anionic surfactants which may be employed are salts of fatty acids, for example C8-C18 fatty acids, especially the sodium or potassium salts, and alkyl, for example C8-C18, benzene sulfonates.

Examples of nonionic surfactants are fatty acid alkoxylates., such as fatty acid ethoxylates, especially those of formula:
R(C2H40)OH

wherein R is a straight or branched C8-C16 alkyl group, pref-erably a Cg-C15, for example C10-C14, alkyl group and n is at least 1, for example from 1 to 16, preferably 2 to 12, more preferably 3 to 10.

The alkoxylated fatty alcohol nonionic surfactant will fre-quently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17, more preferably from 6 to 15, most preferably from 10 to 15.

Examples of fatty alcohol ethoxylates are those made from C12-C15 alcohols which contain about 7 moles of ethylene ox-ide. Such materials are commercially marketed under the trademarks Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an eth-oxylated fatty alcohol averaging 11 carbon atoms in its al-kyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12-C13 alcohol having about 9 moles of ethylene oxide; and Neodol 91-10, an ethoxylated C9-C11 pri-mary alcohol having about 10 moles of ethylene oxide.
Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol trademark. Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated 18_ C12-C15 fatty'. alcohol with an. average of 7 moles of ethylene oxide per Mole of fatty alcohol., Other examples of suitable ethoxylated alcohol nonionic ,sur factants. include Tergitol1.5-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylatesavailable.
from Union Carbide Corporation. Tergitol 15-S-7 is a mixed ethoxylated product of a C11-C15 linear secondary alkanol with 7 moles of ethylene oxide. and Tergitol 15-S-9 is, the- same but with 9 moles of ethylene oxide.

Other suitable alcohol ethoxylated nonionic surfactants are Neodol 45-11, which is an ethylene oxide condensation prod uct of a fatty alcohol having 14-15 carbon atoms and the number of ethylene oxide groups per mole being about `11.
Such products are available from Shell Chemical Company.
Further nonionic' surfactants. are,. for example, Cio-Cle ,'alkyl polyglycosides, such as C12-C16 alkyl polyglycosides, espe.-.
cially.the polyglucosides. -These are especially useful when high foaming compositions are desired. Further surfactants are polyhydroxy fatty acid- amides, -such - as.- Clo-C1e N- (3-methoxypropyl) glycamides and ethylene oxide-propylene .oxide block polymers of the Pluronictype.
Examples of cationic surfactants are those of the quaternary ammonium type.

The total content- of surfactants in the composition is de-sirably 60' to 95wt%, especially.75 to 90wt% -Desirably-'an anionic surfactant is present in an amount, of 50 to 75wt%, the.. nonionic surfactant is present in an amount of 5 to 50wt%, and/or the cationic surfactant is present in an amount of from 0 to 20wt%. The amounts are based on the to-tal solids content of the composition, i.e. excluding any solvent which may be present.

The primary and secondary compositions, particularly when used as laundry washing or dishwashing compositions, may also independently comprise enzymes, such as protease, li-pase, amylase, cellulase and peroxidase enzymes. Such en-zymes are commercially available and sold, for example, un-der the registered trade marks Esperase, Alcalase and Savi-nase by Nova Industries A/S and Maxatase by International Biosynthetics, Inc. Desirably the enzymes are independently present in the primary or secondary compositions in an amount of from 0.5 to 3wt%, especially 1 to 2wt%, when added as commercial preparations they are not pure and this repre-sents an equivalent amount of 0.005 to 0.5wt% of pure en-zyme.

The secondary compositions may, if desired, independently comprise a thickening agent or gelling agent. Suitable thickeners are polyacrylate polymers such as those sold un-der the trade mark CARBOPOL, or the trade mark ACUSOL by Rohm and Haas Company. Other suitable thickeners are xan-than gums. The thickener, if present, is generally present in an amount of from 0.2 to 4wt%, especially 0.5 to 2wt%.
Primary or secondary compositions used in dishwashing inde-pendently usually comprise a detergency builder. The build-ers counteract the effects of calcium, or other ion, water hardness. Examples of such materials are citrate, succi-nate, malonate, carboxymethyl succinate, carboxylate, poly-carboxylate and polyacetyl carboxylate salts, for example with alkali metal or alkaline earth metal cations, or the corresponding free acids. Specific examples are sodium, po-tassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, C10-C22 fatty acids and citric acid. Other examples are organic phosphonate type sequestering agents such as those sold by Monsanto under the trade mark Dequest and alkylhydroxy phosphonates. Citrate salts and C12-C18 fatty acid soaps are preferred. Further builders are; phosphates such as sodium, potassium or ammo-nium salts of mono-, di- or tri-poly or oligo-phosphates;
zeolites; silicates, amorphous or structured, such as so-dium, potassium or ammonium salts.

Other suitable builders are polymers and copolymers known to have builder properties. For example, such materials in-clude appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic and copolymers and their salts, such as those sold by BASF under the trade mark Sokalan.

The builder is desirably present in an amount of up to 90 wt%, preferably 15 to 90 wt o, more preferable 15 to 75 wt o, relative to the total weight of the composition. Further details of suitable components are given in, for example, EP-A-694,059, EP-A-518,720 and WO 99/06522.

The primary and secondary compositions can also independ-ently optionally comprise one or more additional ingredi-ents. These include conventional detergent composition com-ponents such as further surfactants, bleaches, bleach en-hancing agents, builders, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, organic solvents, co-solvents, phase stabilisers, emulsifying agents, pre-servatives, soil suspending agents, soil release agents, germicides, pH adjusting agents or buffers, non-builder al-kalinity sources, chelating agents, clays such as smectite clays, enzyme stabilizers, anti-limescale agents, col-ourants, dyes, hydrotropes, dye transfer inhibiting agents, brighteners, and perfumes. If used, such optional ingredi-ents will generally constitute preferably no more than 15 wt%, for example from 1 to 6wt%, the total weight of the compositions.

Primary or secondary compositions which comprise an enzyme may optionally contain materials which stabilize-the enzyme.
Such enzyme stabilizers include, for example, polyols such as propylene glycol, boric acid and borax. Combinations of these enzyme stabilizers may also be employed. If utilized, the enzyme stabilizers generally constitute from 0.1 to 5wt%, ideally 0.1 to lwt% of the compositions.

The primary and secondary compositions may independently op-tionally comprise materials which serve as phase stabilizers and/or co-solvents. Example are C1-C3 alcohols such as methanol, ethanol and propanol. C1-C3 alkanolamines such as mono-, di- and triethanolamines can also be used, by them-selves or in combination with the alcohols. The phase sta-bilizers and/or co-solvents can, for example, constitute 0 to 1 wt%, preferably 0.1 to 0.5wt%, of the composition.

The primary and secondary compositions may independently op-tionally comprise components which adjust or maintain the pH
of the compositions at optimum levels. The pH may be from, for example, 1 to 13, such as 8 to 11 depending on the na-ture of the composition. For example a dishwashing composi-tion desirably has a pH of 8 to 11, a laundry composition desirable has a pH of 7 to 9, and a water-softening composi-tion desirably has a pH of 7 to 9. Examples of pH adjusting agents are NaOH and citric acid.

The above examples may be used for dish or fabric washing.
In particular dish washing formulations are preferred which are adapted to be used in automatic dish washing machines.

Due to their specific requirements specialised formulation are required and these are illustrated below.

Amounts of the ingredients can vary within wide ranges, how-ever preferred automatic dishwashing detergent compositions herein (which typically have a 1% aqueous solution pH of above 8, more preferably from 9.5 to 12, most preferably from 9.5 to 10.5) are those wherein there is present: from

5% to 90%, preferably from 5% to 75%, of builder; from 0.1%
to 40%, preferably from 0.5% to 30%, of bleaching agent;

from 0.1% to 15%, preferably from 0.2% to 10%, of the sur-factant system; from 0.0001% to 1%, preferably from 0.001%
to 0.05%, of a metal-containing bleach catalyst; and from 0.1% to 40%, preferably from 0.1% to 20% of a water-soluble silicate. Such fully-formulated embodiments typically fur-ther comprise from 0.1% to 15% of a polymeric dispersant, from 0.01% to 10% of a chelant, and from 0.00001% to 10% of a detersive enzyme, though further additional or adjunct in-gredients may be present. Detergent compositions herein in granular form typically limit water content, for example to less than 7% free water, for better storage stability.

Non-ionic surfactants useful in ADW (Automatic Dish Washing) compositions of the present invention desirably include sur-factant(s) at levels of from 2% to 60% of the composition.
In general, bleach-stable surfactants are preferred. Non-ionic surfactants generally are well known, being described.
in more detail in Kirk Othmer's Encyclopaedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems".

Preferably the ADW composition comprises at least one non-ionic surfactant. One class of non-ionics are ethoxylated non-ionic surfactants prepared by the reaction of a monohy-droxy alkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles particularly preferred at least 16 moles, and still more preferred at least 20 moles of eth-ylene oxide per mole of alcohol or alkylphenol.

Particularly preferred non-ionic surfactants are the non-ionic from a linear chain fatty alcohol with 16-20 carbon atoms and at least 12 moles particularly preferred at least 16 and still more preferred at least 20 moles of ethylene oxide per mole of alcohol.

According to one preferred embodiment the non-ionic surfac-tant additionally comprise propylene oxide units in the molecule. Preferably this PO units constitute up to 25% by weight, preferably up to 20% by weight and still more pref-erably up to 15% by weight of the overall molecular weight of the non-ionic surfactant. Particularly preferred surfac-tants are ethoxylated mono-hydroxy alkanols or alkylphenols, which additionally comprises polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or al-kylphenol portion of such surfactants constitutes more than 30%, preferably more than 50%, more preferably more than 70%
by weight of the overall molecular weight of the non-ionic surfactant.

Another class of non-ionic surfactants includes reverse block copolymers of polyoxyethylene and polyoxypropylene and block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane.

Another preferred non-ionic surfactant can be described by the formula:

R10 [CH2CH (CH3) 01 X [ CH2CH2O ] Y [ CH2CH (OH) R2 ]

wherein R1 represents a linear or branched chain aliphatic hydrocarbon group with 4-18 carbon atoms or mixtures thereof, R2 represents a linear or branched chain aliphatic hydrocarbon rest with 2-26 carbon atoms or mixtures thereof, x is a value between 0.5 and 1.5 and y is a value of at least 15.

Another group of preferred nonionic surfactants are the end-capped polyoxyalkylated non-ionics of formula:

R'O [ CH2CH (R3) 0 ] X [CH2 ] kCH (OH) [ CH2 ] j OR2 wherein R1 and R2 represent linear or branched chain, satu-rated or unsaturated, aliphatic or aromatic hydrocarbon groups with 1-30 carbon atoms, R3 represents a hydrogen atom or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl group , x is a value between 1. and 30 and, k and j are values between 1 and 12, preferably be-tween 1 and 5. When the value of x is >2 each R3 in the for-mula above can be different. R1 and R2 are preferably linear or branched chain, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups with 6-22 carbon atoms, where group with 8 to 18 carbon atoms are particularly pre-ferred. For the group R3 H, methyl or ethyl are particu-larly preferred. Particularly preferred values for x are comprised between 1 and 20, preferably between 6 and 15.

As described above, in case x>2, each R3 in the formula can be different. For instance, when x=3, the group R3 could be chosen to build ethylene oxide (R3=H) or propylene oxide (R3=methyl) units which can be used in every single order for instance (PO) (EO) (EO) , (EO) (PO) (EO) , (EO) (EO) (PO) , (EO) (EO) (EO) , (PO) (EO) (PO) , (PO) (PO) (EO) and (PO) (PO) (PO) .
The value 3 for x is only an example and bigger values can be chosen whereby a higher number of variations of (EO) or (PO) units would arise.
Particularly preferred end-capped polyoxyalkylated alcohols of the above formula are those where k=1 and j=1 originating molecules of simplified formula:

R10 [ CH2CH (R3) 01 XCH2CH (OH) CH2OR2 The use of mixtures of different non-ionic surfactants is particularly preferred in ADW formulations for example mix-tures of alkoxylated alcohols and hydroxy group containing alkoxylated alcohols.

In the present invention, if more than one article, for ex-ample a container, is formed at the same time from the same sheet, the articles may then be separated from each other by cutting the portions between them, for example the sealing portions or flanges. Alternatively, they may be left con-joined and, for example, perforations provided between the individual articles so that they can be easily separated a later stage, for example by a consumer. If the articles are separated, the flanges may be left in place. However, de-sirably the flanges are partially removed in order to pro-vide an even more attractive appearance. Generally the flanges remaining should be as small as possible for aes-thetic purposes while bearing in mind that some flange is required if the articles are in the form of thermoformed containers to ensure the two films remain adhered to each other. A flange having a width of lmm to 8mm is desirable, preferably 2mm to 7mm, most preferably about 5mm.

The articles, for example containers, may be packaged in outer containers if desired, for example non-water soluble containers which are removed before the water-soluble arti-cles are used.

The containers produced by the process of the present inven-tion, especially when used for a fabric care, surface care or dishwashing composition, may have a maximum dimension of 5cm, excluding any flanges. For example, a container may have a length of 1 to 5cm, especially 3.5 to 4.5cm, a width of 1.5 to 3.5 cm, especially 2 to 3cm, and a height of 1 to 2cm, especially 1.25 to 1.75cm.

The invention will now be illustrated further by reference to the following non-limiting Examples.

Examples Packages Enclosed by a Water Dispersible Material Powder Formulation The following formulation was prepared by mixing together the indicated components in the weight proportions indicated to prepare a dishwasher powder.

Sodium Percarbonate (DegussaTM Q35) 13.5%
Sodium Tripolyphosphate (Rhodia') 5.5%
Anhydrous Citric acid 3.0%
Trisodiumcitrate 39.6%
Sodium bicarbonate 27.4%
TAED 5.8%
Polyacrylic acid 0.5%
Amylase 0.6%
Protease 1.2%
Nonionic Surfactant 0.5%
Dye 0.15%
Benzotriazol 0.2%
Secondary Component 1) A gelatin ball (solid or hollow) of diameter 11mm having about 0.5g of phthalimidoperhexanoic acid contained therein.
2) A solid ball (0.85g) comprising polyethylene glycol (54%), nonionic surfactant (44%), perfume and dye.

3) A compressed particulate ball with a mass of around 1 -1.3g comprising; lactose (40%), cellulose (18%), sodium phosphonate (6%), protease (13%), amylase (15%), magnesium stearate (0.5%), water, perfume and dye.

Process Method The powder composition and a secondary component were filled into a container using the following procedure.
A Multivac thermoforming machine operating at 6 cycles/min and at ambient conditions of 25 C and 35% RH ( 5% RH) was used to thermoform an anhydrous PVOH film. The PVOH film was prepared by a blown process from granules provided by PVAXX (RTM) ref C120 having a degree of hydrolysis of 88%
and a thickness of 90 Um. When formed the PVOH has a negli-gible water content. The PVOH film was wrapped in a sealed polyethylene container which remained sealed until immedi-ately prior to use. The PVOH film was thermoformed into a rectangular mould of 39mm length, 29mm width and 16mm depth, with the bottom edges being rounded to a radius of 10mm, at 90 C, 600mm Hg. Into the thus formed pocket was added one of the secondary components using a robot arm, afterwards 21g of the powder composition was added. An identical film was placed on top and heat sealed at 100 C in a water seal-ing process. The thus produced containers were separated from each other by cutting the flanges. Each container was rounded and had a full appearance. After a few hours they attained an attractive, rounded appearance.

The invention will now be further illustrated with reference to Figures 1 to 4.

.29-Figures 1 (perspective view), 2 (underneath view) 3 and 4 (both cross-sections) show a water soluble article 1 of the present invention.
The article 1 comprises a primary component 2, in the form of a pocket, and made of water soluble material. The first component 2 contains a secondary component 3, which is op-tionally attached, for example glued, at a point or area on the inside of the primary component 2.

The secondary component as illustrated is in the form of a sphere.

The primary component 2 additionally contains a pow-dered/granulated detergent formulation 4, which is tightly packed therein to hinder movement of the secondary component with the article 1.

The article further comprises.a film 5 of water soluble ma-t-erial which is bonded to the primary component 2 to form the sealed article 1.

The features disclosed in the foregoing description, in the claims and/or drawings may, both separately and in any com-bination thereof be material for realising the invention in diverse forms thereof.

Claims

CLAIMS:

1. A process for preparing a water-soluble article comprising a water-soluble primary thermoformed component and a water-soluble secondary component arranged inside the primary component, which comprises:

(a) forming the primary component into a pocket, by thermoforming in a cavity of a thermoforming mould that also has a recess to receive the secondary component;

(b) introducing the secondary component into the inside of the pocket such that it is received in said recess;

(c) afterwards, introducing contents of the primary component into the pocket; and (d) sealing the primary component, wherein the contents of the primary component are granulated and/or particulate solid(s), and tight packing of said contents into the primary component ensures that the secondary component is fixed in position in the primary component.

2. A process according to claim 1, wherein the primary component is a film.

3. A process according to claim 1, wherein the primary thermoformed component comprises a film.

4. A process according to claim 2 or 3 wherein the primary component is sealed by placing a further film on top of the filled pocket and across a sealing portion and sealing the film and the further film together at the sealing portion.

5. A process according to any one of claims 1 to 4, wherein the secondary component is a compressed solid or a container containing a secondary composition.

6. A process according to any one of claims 1 to 5 wherein the secondary component is a container comprising a polymeric film containing a solid, a gel or a liquid.

7. A process according to any one of claims 1 to 6, wherein the secondary component is in the form of a ball, and adding the secondary component to the mould comprises allowing the ball to roll into the recess.

8. A process according to claim 7, wherein the recess is at the centre of the bottom surface of the mould.

9. A process according to any one of claims 1 to 8, wherein one or both of the primary component and the secondary component comprises a poly(vinyl alcohol).

10. A process according to any one of claims 1 to 9, wherein the article is for use in dishwashing, fabric care or surface care.

11. A process according to claim 10, wherein the primary component comprises a dishwashing, water-softening, laundry or detergent composition.

12. A process according to claim 10 or 11, wherein the secondary component comprises a dishwashing, water-softening, laundry or detergent composition or a rinse-aid.

13. A process according to any one of claims 1 to 9, wherein one or both of the primary component and the secondary component comprises a disinfectant, antibacterial or antiseptic composition.

14. A process according to any one of claims 1 to 9 and 13 wherein the article comprises a refill composition for a trigger-type spray.

15. A process according to any one of claims 1 to 9, wherein the article comprises an agricultural composition.

16. A water-soluble article comprising a water-soluble primary component which is a thermoformed container containing a granulate and/or particulate solid primary composition, and a water-soluble secondary component arranged on the inside of the thermoformed container in a recess thereof, fixing of the secondary component in position in the primary component being ensured by tight packing of said solid primary composition into said primary component.

17. An article according to claim 16, wherein the secondary component is a compressed solid or a container containing a secondary composition.

18. An article according to claim 17, wherein the secondary component is a container comprising a polymeric film containing a solid, a gel or a liquid.

19. An article according to any one of claims 16 to 18, wherein the secondary component is in the form of a ball.

20. An article according to any one of claims 16 to 19, wherein one or both of the primary component and the secondary component comprises a poly(vinyl alcohol).

21. An article according to any one of claims 16 to 20, wherein the article is for use in dishwashing, fabric care or surface care.

22. An article according to claim 21, wherein the primary composition is a dishwashing, water-softening, laundry or detergent composition.

23. An article according to claim 21 or 22, wherein the secondary component comprises a dishwashing, water-softening, laundry or detergent composition or a rinse-aid.

24. An article according to any one of claims 16 to 20, wherein one or both of the primary composition and the secondary component comprises a disinfectant, antibacterial or antiseptic composition.

25. An article according to any one of claims 16 to 20 and 24, wherein the article comprises a refill composition for a trigger-type spray.

26. An article according to any one of claims 16 to 20, wherein the article comprises an agricultural composition.